Process for modifying keratinous material,composition useful therein,and keratinous material bearing thereon said composition

ABSTRACT

THE PRESENT INVENTION RELATES TO A PROCESS FOR MODIFYING KERATINUOUS FIBERS, AND IN PARTICULAR, TO A PROCESS FOR RENDERING KERATINUOUS TEXTILE MAATERIALS RESISTANT TO SHRINKAGE AND TO A PROCESS FOR IMPATING DURABLE PRESS CHARACTERISTICS TO SUCH MATERIALS. THIS PROCESS COMPRISES HEATING THE MATEIAL WITH A POLYTHIOL AND AN ALIPHATIC POLYAMINE-EPICHLOROOHYDRIN RESIN, AND CURING THE POLYTHIOL ON THE MATERIAL. THE PRESENT INVENTION ALSO RELATES TO (1) A COMPOSITIOON USEFUL IN SAID PROCESS, WHICH COMPOSITION CONSISTS ESSENTIALLY OF A POLYTHIOL AND AN ALIPHATIC POLYAMINE-EPICHLOROHYDRIN RESIN, AND (2) KERATINUOUS MATERIAL BEARING THEREON A POLYTHIOL, IN THE CURED OR STILL CURABLE STATE, AND AN ALIPHATIC POLYAMINE-EPICHLOROHYDRIN RESIN.

United States Patent U.S. CL 8-127.6 22 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to a process for modifying keratinous fibres, and in particular, to a process for rendering keratinous textile materials resistant to shrinkage and to a process for imparting durable press characteristics to such materials.

This process comprises heating the material with a polythiol and an aliphatic polyamine-epichlorohydrin resin, and curing the polythiol on the material. The present invention also relates to (1) a composition useful in said process, which composition consists essentially of a polythiol and an aliphatic polyamine-epichlorohydrin resin, and (2) keratinous material bearing thereon a polythiol, in the cured or still curable state, and an aliphatic polyamine-epichlorohydrin resin.

The present invention relates to a process for modifying keratinous fibres, and in particular, to a process for rendering keratinous textile materials resistant to shrinkage and to a process for imparting durable press characteristics to such materials.

A number of shrink-resist processes and durable press processes for keratinous textile materials are known, some of which comprise the application'of a resin to the material, which may be in fabric or fibre form. Shrink-resistant processes stabilize the dimensions of the material against shrinkage due to felting or relaxation. Durable press processes stabilize the desired shape and the surface smoothness of the material against deformation in the presence of aqueous solutions.

A desirable, though not essential, feature of shrink-resist and durable press processes is that the material so treated should be washable in domestic washing machines, and this sets a severe test for the durable press and shrink-resist treatments. Some known treatments result in a uniform but inadequate improvement to the resistance of the material to shrinking whilst others are capable of imparting a very high but irregular resistance. In the latter case, under vigorous mechanical action in a washing machine, felting shrinkage at exposed edges of the garment, such as cufis, can be greater than at less exposed parts.

One of the attractions of keratinous fibres, particularly woollen fibres, is their excellent handle, and a serious disadvantage associated with many of the resins hitherto used in shrink-resist and durable press processes is the harsh handle imparted to the fibre and fabric containing the fibres. Attempts to overcome this harsh handle by the use of softeners have often been unsuccessful in that they reduce the effectiveness of the resin.

In our French Pat. No. 2014611 we have described and claimed a process for modifying keratinous material which comprises treating the material with a polythiol having at least two thiol groups per molecule and containing and curing the polythiol on the material.

These polythiols can be used to impart durable press effects and resistance to shrinkage without impairing the handle of the treated material.

We have now found that the efl'ect of these polythiols is improved to a surprising extent if they are used in the presence of an aliphatic polyamine-epichlorohydrin resin.

There is accordingly provided a process for modifying keratinous material which comprises treating the material with a polythiol as aforesaid and an aliphatic polyamineepichlorohydrin resin, and curing the polythiol on the material.

We have also found that the aforesaid agents, viz. the polyamine-epichlorohydrin resin and the polythiol, may be applied to keratinous fibres by exhaustion from an aqueous medium.

The term exhaustion as used herein means the method of treating the fibres with an aqueous solution or emulsion of the polythiol or polythiol-resin mixture until a major proportion of the polythiol or the mixture is deposited on the fibres. It is believed that, in addition to promoting the curing of the polythiol, the polyamine-epichlorohydrin resin also promotes exhaustion of the polythiol.

Aliphatic polyamine-epichlorohydrin resins are known materials. They are cationic, polymeric, and crossable; they are usually water-soluble and are usually made by reaction with epichlorohydrin of a polyalkylenepolyamine such as a poly(ethyleneimine) and particularly an amine containing from 2 to 8 alkylene groups per molecule, sometimes in the presence of a base, followed by acidification. The term aliphatic polyamine-epichlorohydrin resin also includes those derived from more complex amines. In particular, there may be used amines made by heating polyalkylenepolyamines with dicyandiamide. with liberation of ammonia; poly(aminoamides) made from polyalkylenepolyamines and aliphatic dicarboxylic acids or amide-forming derivatives thereof, e.g. their dimethyl ester. Other examples are adducts of polyalkylenepolyamines with stoichiometric deficits (calculated on the basis of one epoxide group per amino hydrogen atom) of monoor poly-1,2-epoxides.

The precise structure of the amine-epichlorohydrin resins has been the subject of some controversy. It is believed, although the usefulness of this invention does not depend on the truth of this belief, that they contain hydroxyazetidinium ions, and that linking of chains through nitrogen atoms occurs, i.e. the resins, acidifiedwith, for example, hydrochloric acid, contain structures of the type It possible that they also contain lj-chlorohydrin groups Use of"these amine-epichlorohydrin resins for shrinkproofing-woblhas already been proposed. However, they have little-effectunless the wool has first been chlorinated. In coritradistinction, prechlorination of the wool is not necessary for carrying out the process of this invention. Further, the amount of the amine-epichlorohydrin resins used in the present process can be small, often only cata- .lyti'c proportions being used. It is evident therefore, that the success of 'the present process is not attributable merely to any inherent shrinkproofingelfect of the polyamine-epichlorohydrin resin.

v Amine-epichlorohydrin resins which have been found most satisfactory for use in the present process are obtainable by reaction of a saturated aliphatic dicarboxylic acid of 3 't'o20 carbon atoms (or an amide-forming derivative thereof) and a polyalkylenepolyamine containing 2 to 8 alkylene groups, reaction of the resultant poly- (aminoamide) with epichlorohydrin, and acidification to form a water-soluble cationic resin. An example of a commercially-available resin which has proved especially useful is obtained by forming an amide such as is repre sented by the equation followed by treatment with epichlorohydrin and then acidification.

Examples of aliphatic dicarboxylic acids from which these epichlorohydrinpolyamine resins can be derived are malonic, succinic, adipic, and azelaic acids; examples of their amide-forming derivatives are their dirnethyl esters; there may also be used mixtures of such acids or esters.

One or more polyamines can be used in the formation of vthese epichlorohydrin-polyamine resins; specific examples, are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and N,-bis(3- aminopropyDmethylamine. Suitable amines preferably contain at least 2 amino groups separated by a hydrocarbon group having the general formula C,,,H where a is at least 2 and -at most 4. The term keratinous material" as used throughout this spec fication includes all forms of kcratinous fibres or fabricsand garments made therefrom, e.g. fleeces, tops, ca rd sliver, noils, yarns, threads, pile fabrics, non-woven fabrics, woven fabrics, and knitted goods. In most cases the treatment will be applied to fabrics or made-up garments though it is quite feasible, and may 'be desirable in some c rcumstances, to treat fibres in the form of tops, for example. The material to be treated can consist either wholly of keratinous fibres or of blends of these fibres withsynthetic fibrous and filamentary material, in--.

cluding polyamides, polyesters, and poly(acrylonitrile), and with cellulosic, including regenerated cellulosic, material. In general, however, the material should contain at least 30% by weight of kcratinous fibres and the most useful effects are obtained with 100% kcratinous fibre material.

The kcratinous material may be virgin or reclaimed and is preferably sheeps wool. It may, however, also be derived from alpaca, cashmere, mohair, vicuna, guanaco, camel hair, and llama, or blends of these materials with sheeps wool.

The treatment according to the invention, whether to achieve shrink-resist or durable press effects, provides fabrics or garments which will withstand washing in machines without the development of local areas of felt- 4 I f a ing and still retain their orginial dimensions and shape. In addition to having an excellent hag d l e tl 1 e t r gt ed material also has good recovery from wrinkling, which is an important attribute in many garments but especially in trousers, where there is a strong tendency to wrinkles in the areas of the knee and back of the knee.

Thepolythiols usually contain up to isix thiol groups per average molecule and especially good results have been obtained with those containing three or four thiol groups per average molecule. a i r The preferred polythiols arethose'having .a molecular weight between 400 and 10,000, particularly those; of formula i -j n, p, and q each represent positive-integers,

m is an integer of at least 1 and may have different values in each of the p and (q'-1 chains,

nis atmost 2, v M

p is at least 2 and at most 6,

q is such that (p+q)' equals at least 3 arid at most 7,-

each alkylene group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms,

R represents an aliphatic radical containing at least (but preferably not more than 6)carbon atoms,""

and X represents an aliphatic radical containing at least one thiol group.

The oxyalkylene units in individual poly('oxyalkylene) chains may be different. They may be substituted', if desired, by e.g., phenyl or chloromethyl groups.

There may thus be used the partially or fully esterified compounds of the formula in which R, alkylene, m, p, and q have -;the meanings previously assigned, and r is a positive integer which'may be as high as 18 or even 24.

Further preferred are esters of the formula u is a positive integer of at most 2 I p is an integer of at least 3 and' 'at most 6,,

and R represents an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms.

alkylene and m have the meanings previouslyassi'gned,

drins)s, butane-1,2-diol, butane-1,3-diol,. butane-l,4-diol,. butane-2,3-diol, poly(oxy-l,l-dimethylethylene) glycols,-

poly(tetrahydrofuran)s, glycerol, l,l,1-trimethylolethane, 1,1,l-trimethylolpropane, hexane-1,2,5 triol, hexane-1,2,

6-triol, pentaerythritol, dipentaerythritrol, mannitol,-sor-- bitol, and adducts of alkylene oxides with ammonia or amines, such as diethanolamine and tetrakis(2-hydroxyethy1)ethylenediamine. Suitable alkylene oxides include ethylene oxide, propylene oxide, and, less preferable the butylene oxides, cpichlorohydrin, or tetwhydrofurart. If

. aa CH T T C HuL O. C 0.0.HmSH

in which m and u have the meanings previously assigned, and t is an integer of at least 2 and at most 3.

Polythiol esters most preferred for the purposes of the present invention are those obtained from glycerol, propylene oxide, and thioglycollic acid, i.e. of formula where m has the meaning previously assigned, having a molecular weight within the range 1000 to 6000. Such esters are commercially available.

The second class of thiol-terminated poly(alkylene oxides) includes those ethers of formula in which R; denotes OH, (Oalkylene) OH,

O.CO.C,,H ,,SH,

or --(Oalkylene) O.CO.C,,I-I ,SH,

R, alkylene," m, p, q, and u have the meanings previously assigned, and

v is an integer of at least 1 and may have different values in each of the p chains.

The oxyalkylene units in the individual poly(oxyalkylene) chains may likewise be different, but are preferably the same, and may be substituted if desired by e.g., phenyl or chloromethyl groups.

Preferred among such ethers are those which are also of formula 1 (oalk 1ene) 0CH,CH0H,sH

in which alkylene, R m, R p, and q have the meanings previously assigned, and further preferred are those of the formula in which R t, m, and p have the meanings previously assigned.

The ethers of formula II in which R denotes OH may be prepared in a known manner by reaction of an alkylene oxide with a polyhydric alcohol, etherification of the hydroxyl groups of the product with epichlorohydrin, and treatment with sodium hydrosulphide to replace the chlorine by a sulphydryl group (see US. Pat. 3,258,495, and United Kingdom Specifications 1,076,725 and 1,144,- 761). In many cases the average number of thiol groups per molecule is not an integer but, for example, may be 2.6. This is attributable partly to the replacement of the chlorine atom by the SH group not going to completion, and partly to side-reactions: for example, the chlorohydrin ether obtained by reaction with epichlorohydrin may also react with epichlorohydrin, so forming an ether which contains two replaceable chlorine atoms per hydroxyl group originally present in the polyhydric alcohol.

Ethers of formula R.j o onmmo cmt znernsn l L 0 ounmon l m in which R 1, m, v, and p have the meanings previously assigned, may likewise be used.

Ethers of formula II in which R; denotes ---(Oalkylene) ,OH

where m has the meaning previously assigned, especially such ethers having a molecular weight within the range 700 to 6,000.

The ether-esters of formula II in which R, denotes O.CO.C,,H ,,SH or --(Oalkylene) 0.CO.C H SH are obtainable by esterification of the corresponding alcohol with a mercaptocarboxylic acid HOOCC H- SH.

The epichlorohydrin-polyamine resins usually dissolve in water present in the treatment bath. Many of the polythiols are insoluble in water but can, as has already been indicated, he applied as aqueous dispersions or emulsions in which the epichlorohydrin-polyamine resin may for convenience be included. The polythiols may also be applied to fabrics and garments from organic solvents, for example lower alkanols such as ethyl alcohol, lower ketones such as ethyl methyl ketone, benzene, halogenated hydrocarbon solvents, especially chlorinated and/or fluorinated hydrocarbons containing not more than three carbon atoms such as the dry cleaning solvents carbon tetrachloride, trichloroethylene, and perchloroethylene.

The mixture of the polythiol of the aliphatic polyarnineepichlorohydrin resin used in the process according to the invention, as well as inhibiting or preventing felting shrinkage, also inhibits or prevents relaxation shrinkage, which is an important problem associated with knitted goods.

The amount of polythiol used depends upon the effect desired. For most purposes from 0.5 to 15%, based on the weight of textile material is preferred; stabilization of knitted fabrics usually requires from 1 to 10% polythiol. A high level of shrink-resistance, crease-setting, and substantial resistance to wrinkling can be achieved on woven fabrics with rather smaller quantities, especially from 1 to 5%. The amount of the aliphatic polyamine-epichlorohydrin resin which can be used depends to an important extent upon the nature of the polythiol present. In general from 0.1 to 1.0% of polyamine-epichlorohydrin resin based upon the weight of material is sufiicient but the amount must be carefully selected to give the best result. Thus the examples illustrate that if Polythiol A (see below) is the olythiol and Polyamine resin I is the polyamine-epichlorohydrin resin good results are obtained when 0.1 to 0.2% by weight of Polyamine resin I on the weight of fabric is employed. Higher quantities did not appear to confer any benefit. Usually, the ratio of polythiol to polyamine-epichlorohydrin resin is from 7.5 to

25:1 by weight. The handle of the treated material will,

of course, depend on the amount of the agents employed and by simple experiment the least amount required to give the desired effect may readily be determined. The construction of the fabrics also influences the amount of polythiol required.

The desired effects are not fully obtainable until substantially all the polythiol on the material has been cured. The curing reaction is greatly accelerated by the use of the epichlorohydrin-polyamine resin and generally it is preferred to add it to the material to be treated at the same time as the polythiol is applied although it may be added before or afterwards if desired.

Curing of the polythiol is also assisted by using elevated temperatures and if especially rapid results are required then temperatures in the range 30 to 180 C. may be used. High humidities also tend to accelerate the curing: autoclaving of the treated material may therefore be desirable.

Curing is preferably carried out under neutral or slight- 1y alkaline conditions (e.g. in the presence of sodium pyro phosphate or sodium bicarbonate), say, at a pH in the range 7 to 9, and may also be accelerated by means of a freeradical catalyst, e.g. hydrogen peroxide.

The polythiol and the epichlorohydrin-polyamine can be applied to the keratinous material in conventional ways. For example, where wool tops or where fabric is to be treated, they may be padded on or the material may be immersed in a bath containing the agents. If garments or garment pieces are to be treated then it is convenient to spray them with the agents, and more convenient still to tumble them with the agents in an organic solvent. For the latter method a dry-cleaning machine using a drycleaning solvent is a particularly useful apparatus.

The polythiol and the epichlorohydrin-polyamine resin can, as already indicated, he applied to the fabric by exhaustion, and such a treatment can be applied before, simultaneously with, or after dyeing. Exhaustion can be carried out at a pH in the range 2-10, especially 4-8, and at any temperature from room temperature (say, C.) to 100 C., and will normally be complete after l-2 hours. The process is especially advantageous in that exhaustion may be carried out at temperatures up to 50 C. with substantially complete exhaustion of the agents.

If a shrink-resist treatment is required, then it is usually convenient to apply the reactants to the fabric although, as previously stated, they may be applied to fibres in the form of tops or card sliver. Setting, including flat-setting of the fabric, whether carried out before or after treatment with the polythiol and the epichlorohydrin-polyamine resin, may be effected using any of the known methods, for example by means of setting agents, such as reducing agents, bases, water, and superheated steam. Monoethanolamine sesquisulphite is the most frequently used and may be used in association with a swelling agent, e.g. urea. In another method the material is impregnated with a swelling agent and an alkanolamine carbonate, e.g. urea and diethanolamine carbonate, dried, and semi-decated. Of course, if desired, the fabric may be set in the presence of the agents, thus effecting setting and shrinkproofing treatments simultaneously.

If a durable press treatment is required, there are a number of ways this may be achieved. One method is to treat the material with the agents, make the material up into garments or garment pieces and insert therein pleats or creases, using reducing agents, bases, or superheated steam as setting agents. The agents may likewise be applied to the fibres at any stage during the manufacture of the fabric, eg. in the form of tops or yarns. If desired, substances which block the thiol groups of the wool, e.g. formaldehyde or higher aldehydes, may be applied to the creased or pleated garments after curing the poly thiol.

Another method of applying the polythiol to obtain a durable press effect comprises treating the made-up garment or garment piece, which is already in the desired configuration, e.g. has creases or pleats imparted thereto, with the polythiol dissolved in an organic solvent. In this method it is essential that the polythiol is applied in an organic solvent because treatment with aqueous systems would remove the creases or pleats already set in the fabric.

An alternative method, which is primarily concerned with the production of durable press pleats or creases only, comprises impregnating the fabric with the agents in the area where a fold, such a crease or pleat, is to be inserted, imparting the desired configuration, and maintaining it in this position whilst heat and pressure are applied.

A method for flat-setting and shrinkproofing keratinous fabrics comprises treating the fabric with a setting agent and setting it in a flat configuration by heating the fabric while wet, impregnating it with an aqueous emulsion or dispersion of the agents, drying the fabric and curing the polythiol. Finally the fabric is made into garments, and creases or pleats set therein, if desired, by steaming in the presence of a setting agent such as monoethanolamine sesquisulphite.

Milling effects can be imparted, especially to knitted woollen goods, by tumbling them in a dry-cleaning solvent containing the reagents and a controlled amount of water.

It has also been found that the exhaustion treatment can be combined with dyeing with any anionic dye which will exhaust onto the wool. Commercially available acid levelling dyes can be used, for example Supracid Yellow R (Francolor, Erio Fast Floxine KL, Erio Fast Blue ZGL, and Solophenyl Turquoise Blue GL (Ciba-Geigy), Lissamine Fast Red B and Solway Blue PFN (ICI), and A20 Rubinole 3 GP (Sandoz). Suitable premetallized dyes include Cibalan Orange G and Irgalan Brown GRL (Ciba-Geigy), Carbolan Green G 125 (ICI), Lanasyn Yellow 2RL (Sandoz) and Neolan Red BRE (Ciba- Geigy). Suitable reactive dyes which include Lanasol Yellow 4G, Lanasol Red 6G, and Lanasol Blue 3G (Ciba- Geigy) and Procilan Red GS (ICI) can also be used. Acid milling dyes, for example, Polar Brilliant Red 3BN (Ciba-Geigy) can also be used.

The invention will now be illustrated by reference 'to the following examples. Unless otherwise specified, parts and percentages are by weight, and temperatures are in degrees centigrade.

The polythiols used were prepared as follows.

POLY'I'HIOL A A mixture of 800 g. (0.2 g.-mol.) of a triol of average molecular weight 4,000 made from glycerol and propylene oxide, 55.2 g. (0.6 g.-mol.) of thioglycollic acid, 5 g. of toluene-p-sulphonic acid and 350 ml. of toluene was heated to reflux with stirring in an atmosphere of nitrogen. Water (10.8 ml., 0.6 g.-mol.) formed during the reaction was removed as its azeotrope with toluene. The mixture was cooled and washed with water, and the organic layer was separated. On removal under vacuum of the solvent from the organic layer there remained 793 g. (94% of the theoretical yield) of the desired tris(thioglycollate) (Polythiol A), having a thiol content of 0.59 equiv./kg.

'POLYTHIOL B This is a poly(2-hydroxy-3-mercaptopropyl) ether prepared from a glycerol-propylene oxide adduct having an average molecular weight of 4,800, epichlorohydrin, and

9 sodium hydrosulphide. It has a thiol content of 0.32 equiv/kg.

The polyamine resins were:

Polyamine resin I Polyamine resin II Three moles of diethylene triamine are first heated with 1 mole dicyandiamide and then with 2 moles of dimethyl adipate. This reaction productis then heated with 4.5 moles of epichlorohydrin, and the resin is finally diluted with water to give a 20% solution of Polyamine resin II.

Polyamine resin III An epoxide (68.5 g.), having an epoxide equivalent weight of 685 and which has been made by reaction of 2,2-bis(4-hydroxyphenyl)propane first with epichlorohydrin and then with a mixture of l-aminoeicosane and l-aminodocosane, is dissolved in 37 g. of isopropanol and heated to 88. Then a poly(aminoamide) (24.7 g.) prepared from polymerized linoleic acid and diethylenetriamine (0.1 amino group equivalent), dissolved in 15 g. of isopropanol, is added dropwise to the epoxide solution. Afterwards the mixture is stirred under reflux for 5 hours and 1.85 g. of epichlorohydn'n is added. Glacial acetic acid (16 g.) in 312 g. of water is then added and the mixture is stirred until it has cooled. A liquid of low viscosity is obtained, having a 20% content of resin III and a pH value of 4.6.

The emulsions containing the polythiol were prepared by dissolving 0.5 part of sodium carboxymethylcellulose in 44.5 parts of water at 70 to 80", allowing the solution to cool, adding 50 parts of the polythiol and 5 parts of Wetting Agent I, and stirring with'a high speed mixer for 5 minutes.

a EXAMPLE I This Example illustrates the pronounced eifect a Polyamine polythiol (Polythiol A) to confer on a wool fabric resistance torelaxation and felting shrinkage; This Example also illustrates how critical are the amounts of the polyamine-resin needed for the best results to be'obtained.

Samples of knitted double jersey'wool fabrics known under the name Ponte di Roma cru were treated in a padding machine with aqueous emulsions containing different proportions of dispersed Polythiol' A and dissolved Polyamine resin I and sodium bicarbonate. The pickup was 150%, and the emulsions employed contained the following ingredients (in grams) made up to -1 litre with water:

1 2 3 4 5 Polythiol A 2o 19. a .18. 1 1s 1a Polyamine resin 1. 0 0. 7 1. 3 2. 0 4. 0 Wetting agent II- 2. 5 2. 6 2.5 2.5 2. 5 Sodium bicarbonate 2 2 2 2 2 samples were then washed at 40 10 Relaxation shrinkage 500 g. of the samples were placed with 500 g. of cotton make-weights into a Cubex laboratory washing machine. The total load in the machine, amounting to 1 kg. was Washed for 15 minutes in 15 litres of phosphate buffer (pH 7) heated to 40, and centrifuged for 10 seconds. The samples were then dried flat in an oven at 70 and were conditioned for 16 hours at a temperature of 20 and a relative humidity of The dimensions of the fabric were measured before and after washing and the linear shrinkage in length and width was calculated. The area shrinkage was calculated from the changes in linear dimensions.

Felting shrinkage This was determined on the relaxed fabric by washing the samples for a further 4 hours and calculating the shrinkage results on the dimensions of the relaxed fabric.

The following results were obtained:

Percent Polyamine Area shrinkage! resin I K (on weight Relaxaof fabric) tion Polythiol A (on weight of fabric) male It will beseen that when 0.1 to 0.2% by weight of Polyamine resin I was used there was a major reduction in both relaxation and felting shrinkage but when more than 0.2% was used both types of shrinkage also increased.

EXAMPLE 2 The fabric employed was a wool flannel weighing ap proximately 170 g. per square metre. Samples were padded to 140% pickup with the following formulations (Polythiol A was added as an aqueous emulsion), both of which also contained suflicient sodium bicarbonate to bring their pH up to 7.8.

(Wetting Agent III is an adduct of p-octylphenol with 8 mol. of ethylene oxide.)

After being dried at for 15 minutes, the samples were heated for 5 minutes at or steamed for 2% minutes with a steam iron to complete the curing. The in an English Electric Reversomatic washing machine set on programme 5 with the timing control set on No. 1. The washing liquor was an aqueous solution of soap flakes (2 g. per litre) and anhydrous sodium carbonate (0.8 g. per litre), and the liquor/sample ratio was about 30:1. The samples were rinsed in cold water, spun in the machine, and then dried for 30 nun' utes in a Parnall tumble drier on full heat.

RESULTS Shrinkage in area (percent) 011 Formulation Curing washing 6 5 minutes at 140 4. 5 6-- 2% minutes steami Z. 5 minutes at 140 2% minutes steaming 1 1 EXAMPLE 3 "Other formulations employed were as follows (the'figures indicating the weight taken in grams):

Polythiol-A 27. 25. 0 Polyamitle resin 1. 2. 7 0 Polyamine resin III- 0 6.0 Wetting agent II 2 2 Water to 1 litre.

take and then pressed in a Hoffman press at 120 for 2% minutes under a pressure. of 1 kg. per sq. cmnNext, they were stored for days at room temperature, washed in the Cubex" machine as described in Example 1, and dried 'ina'n 'oven at 70. The table shows the results obtained.

Total shrinkage Alter shrinkage after washing Formulation relaxation after washing and drying N Ont-Negative values indicate expansion of the fabric..-

EXAMPLE 4 I This Example illustrates the great resistanceof a flatset woven 'wool fabric to felting shrinkage and loss of set when treated with Polythiol A in the presence of a small proportion of Polyamine resin 1. V

For the purpose of this test an undyed. woven fabric of plain weave was employed. The fabric wa's" constructed from 80 tex warp and weft yarns having '12 ends and 12 picks per cm. The fabric had a weight of 1 90 'g .'/s q. m.

Samples of the fabric were flat-set by padding with 2% by weight of monoethanolamine sesquisulphite=followed by semi-decating' (5 minutes steam, 2 minutes vacuum). An aqueous emulsion of Polythiol A containing sodium bicarbonate and Polyamine resin I was paddeditif 'l50% pickup on to the fabrics, the concentrationbeing adjusted to give 2.5% Polythiol A, 0.25%, Polyamine resin I, and 1.0 or 2.0% sodium bicarbonate on-the weight of fabric. The emulsion also contained 12% of .Wetting Agent H as emulsifying agent, calculatedfon .the weight of the polythiol. Another series of fabric samples was treated with a similar emulsion but containing no Holy,- amine resin I. The samples were washed in. a Bendix MRE rotating drum washing machine for onehour in phosphate buffer of pH 7 at 40 using a liquorzgoods ratio of 22:1. .After washing the samples, they werecen: trifuged for 30 seconds. Some of the samples were washed for a total of 10 hours to detect any break-down in the effect of the agents on prolonged washing.

The following results were obtained.

1.0% sodium bicarbonate 2.0% sodium bicarbonate 12 These results show that, even after the samples had been washed for 10 hours under the vigorous conditions existing in a domestic washing machine, the improved performance of the polythiol was still evident.

. EXAMPLE 5 ample 2 The shiinkagein area on washing after storing for and '7 days was,respec,tiyely, 6.4 and 5.0%. Untreated wool shrank by 22%.

EXAMPLE 6 This Example illustrates impregnation with two baths. "'Wool-flannel'waspaddedto' 300% 'uptake with a perchloroethylene solution 'ofiPoly'thiol A so as to leave 3% of- Polythiol A on' the weight of wool. The treated fabric dried 'in an oven at at its original dimensions. Portions of the flannel were then padded to uptake with a 18%" aqueous solution or Polyamine I containihgjlo 'g. per litre of sodium bicarbonate. The cloth was dried at 70 C. in. an oven at its original dimensions, and. washed by the procedure described in Example 3. The shrinkage in area was 4.5%; untreated wooltlannel shrank by 19.5%, while samples treated only with the polythiol shrank by 16%.

T-EXAMPLE, 1

, A double jersey Ponfe di Roma fabric, knitted from 32's worsted'.yarn 'to .cover factor-of 1.35 with a run-in ratio of 111.3," was treated at a liquor ratio of 25:1 and at a temperature of 9 531 003; with an aqueous emulsion containing the ingredients specified in the following tab1e,'the percentages by w'eiglitbeing calculated on the weight of the fabric. Deposition "bf polythiol' from the emulsionwa's followed by measuring the turbidityvof the emulsion "Si g a Spectrophotometer. After deposition of the polythiol had been completed, the fabric was spun in a centrifuge, dried, and autoclaved at a steam pressure ofl kg Jsq. for 5 minutes. 7

Samples of the treated fabric were then-washed forl hour'ln 'a. Bendix MRE washing machine at a liquor: gQqds',r a tip.of.22:1. An tmtreated sample of the fabric was washed for comparison. The results obtained were as .follows: Treatment: Percent total area shrinkage Polythiol A (4%), Wetting Agent II Untreated 49 'EXAMRLE 8..

Samples of a singlejersey fabric, knitted from 2/24s worsted yarn to a cover fabric of 1.1, were treated by exhaustion with thecompositions specified in the following table (Polythiol A bein g added as an aqueous emulsion) at .9 095 and at aliquorzgoods ratio of 50:1. After exhau'stion was complete the treated fabric samples were spun dry, soaked for 20-30 minutes in a solutionv containing 10% sodium carbonate on the weight of fabric at a liquorzgoods ratio of 50:1, and oven-dried. The samples 1 3 were then washed for 1 hour in a 15 liter Cubex" at 40. The following results were obtained:

Percent Total Polythlol area Treatment exhausted shrinkage 5%Polythiol A plus 0.25% Polyamine resin I 100 -2 5% Polythiol A plus 0.5% Polyamine resin I 100 -4 5% Polythiol A plus 0.75% Polyamine resin I 100 -l 5% Polythiol A plus 0.25% Polyamine resin 11.... 100 1 6% Polythiol A plus 0.5% Polyamine resin II 100 l 5% Polythlol A plus 0.75% Polyamine resin IL.-- 100 1 6% Polythlol A (no polyamlne-eplchlorohydrin resin added) 5O Untreated 67 l Negligible.

EXAMPLE 9 The single jersey fabric of Example 8 was treated by exhaustion at the boil with the following composition, the

polythiol being added as an aqueous emulsion.

Percent Polythiol A Polyamine resin I 0.25 Lanasol Red 2G 1.5 Acetic acid 1.5

The treated fabric was then soaked for 60 minutes in an aqueous solution containing 3% of sodium carbonate (calculated on the weight of fabric), spun in a centrifuge, and dried. A level-dyed fabric having excellent shrinkresist properties was obtained.

EXAMPLE 10 EXAMPLE 11 Example 9 was repeated except that in place of Polythiol A there was used the same amount of Polythiol B. This polythiol performed in the same way as did Polythiol A, and the resulting fabric exhibited a 1% area felting shrinkage after washing for 1 hour in a Cubex."

EXAMPLE 12 Samples of a scoured single jersey fabric knitted from 2/24s worsted yarn to cover factor of 1:1 were treated by exhaustion with the compositions specified in the following table (Polythiol A being added as an aqueous emulsion) at a temperature of 22 and at a liquorzgoods ratio of 50:1. The amounts of the polythiol and polyamine resin are expressed in terms of the weight of the fabric. After treatment was complete the samples were spun dry, soaked for 20-30 minutes in a solution containing 10% sodium carbonate on the weight of fabric at a liquor:goods ratio of 50:1, and oven-dried. The samples were then washed for 1 hour in a 15 litre Cubex at 40. The following results were obtained:

\ Negligible.

14 EXAMPLE 13 The scoured single jersey fabric of Example 12 was treated by exhaustion with an aqueous emulsion containing 5% by weight, calculated on the weight of the fabric, of Polythiol A, and 5% by weight, calculated on the weight of the polythiol, of Polyamine I. Exhaustion was carried out at 50 and was found to be complete after 15 minutes. The fabric was rinsed, and then treated with hydrogen peroxide and/or sodium pyrophosphate as shown in the following table at a temperature of 50 for 30 minutes to effect curing. The samples were then rinsed and dried.

The samples were afterwards washed for 1 hour in a 15 litre Cubex" and the following results were obtained:

The scoured single jersey fabric of Example 12 was treated by exhaustion as described in Example 13. Instead of the peroxide/pyrophosphate curing treatment the fabric was treated with a mordant composition comprising sodium dichromate (1.5% by weight based on the weight of the polythiol and the resin) and formic acid (3.0% based on the weight of the polythiol and the resin) at the boil at a liquor: goods ratio of 50:1 for a period of 45 minutes. Sodium metabisulphite (1% by weight) was added to the bath and boiling was continued for a further 15 minutes. The bath liquor was drained away and the fabric was treated with the following dye composition, the percentages being the weights calculated on the weight of the fabric:

(Wetting Agent III is an amphoteric polyglycol ether derivative.)

The bath was maintained at 50 for 30 minutes and then maintained at the boil for minutes. A yellow-dyed fabric was produced which exhibited a 5% area felting shrinkage after washing for 1 hour in a 15 liter Cubex."

We claim:

1. Process for modifying keratinous material, which comprises treating the material with (i) about 0.5 to 15% its weight of a polythiol having at least two thiol groups per molecule and containing (a) a radical of a polyhydric alcohol,

(b) bound to this radical, at least two poly (oxyalkylene) chains,

(c) bound through oxygen atoms to carbon atoms in the said poly (oxyalkylene) chains, at least two residues chosen from the group consisting of acyl radicals of thiol-containing aliphatic carboxylic acids and the radicals, after removal of the hydroxyl groups, of thiol-containing aliphatic alcohols, and

(ii) about 0.1 to 1% of its weight of an aliphatic polyamine-epichlorohydrin resin, and curing the polythiol material.

2. Process according to claim 1, wherein the polythiol contains from three to six thiol groups per molecule.

3. Process according to claim 1, wherein the polythiol has a molecular weight of between 400 and 10,000.

4. Process according to claim 1, wherein the polythiol is ofthe formula q has a value that (p-l-q) equals at least 3 and at m0st 7, each a y snsf ersm sqnta n ayhai .q atlea t 2 and at most 6 carbon atoms between consecutiv oxygen atoms, a. a a

R represents an aliphatic radical containing at least 2 carbon atoms,

and X represents an aliphatic radical-containing-at least one t h iol group.

5. Process according to claim 4, wherein the polythiol is of ts mvl Oalkylene) OH] O lkylene O.CO.C,H SH

in which R, alkylene," m, p, and q have the meanings assigned in claim 4,

and r is a positive integer of from 1 to 24.

6. Process according to claim 5, wherein the polythiol is of the formula .l il in which alkylene" and m have the meanings in claim 4,

u is a positive integer of at most 2, r'.;" H

p; is an integer of at least 3 and at most 6, I Y

and R represents an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms.

7. Process according to claim 6, wherein tthepolythiol is of the formula on,- o o,H,.).,,o.o0.o.H=,,sH

H-(O o,rr,,$.,.o.oo.o.H,.,s1r

Hroo,H,,- ..0.oo.o.-H,.sH,,,

in is an integer of at least 1 and may have different values in each of the p and (q-l) chains,

u is a positive integer of at least 3 and at most 6-,

and t is an integer of at least 2 and at most 3;

16 where m has the meaning'assigned in claim 4, having-a molecular weight within the range'1,000 to 6,000.

9. Process according to claim 1, wherein the polythiol of the'formula R- fdsllr ylene) 0H, 011C111 S H] i .v m I p in which v v R; denotes OH, (O'--alkylene),,OH,

V v ,O.CO .C H SH,

or -(Oalkylene) O.CO.C H SH,

R, alkylene, m, p, and q have the meanings assigned in claim 4, H leis a positive integer of at least 3 and at most 6, and v is an integer of at least l and may have different values in each of the p'chains. i

10. Process according to claim 9, wherein the p yt iql is also of the formula V 1 r Oalkylene);O on; once, s n] J m R! P in which alkylene," m, and p have the meanings assigned in claim 4, R represents an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms, and R denotes -O H, (O-alkylene) OH,

11. Process according to claim 10, wherein the polythiol is also of the formula [Rig- 10C HMmO'CHaCHCHzSH] in which m isan integer of at least 1 and may have different values in each of the p and ((1-41) chains,

t is ;a positive integer of at least 3 and at most 6.

and p and -R have the meanings assigned in claim 6.

12. Process according to claim 11, wherein the polythiol is also of the formula CHE-(O CrHQmOCHAIEHCHzSH v I r 0H K-(OQtEMOCHzCHCHzSH H 'orr; -(o o,H'. ...ocH,( :HoHrsH Q A 0H v where m is an integer of atleast 1 and may have different values in each of the p and (ql) chains and has a moleg ular weight in the range 700 to 6,000.

13. 'Process according to claim 1, in which the aliphatic polyamine-epichlorohydrin resin is one made by reaction of a polyalkylenepolyamine containing from 2 to 8 alkylene'groups "with epichlorohydrin, followed by acidificati o n.

' 14. Process according to claim 1, in which the aliphatic polyarnine-epichlorohydrinresin is one made by heating a-polyalkylenepolyamine containing from 2 to 8 alkylene groups with dicyandiamide, ammonia being liberated, followed by reaction with epichlorohydrin and by acidificat-ion. 1

15. Process according to claim 1, in which the aliphatic polyamineepichlorohydrin resin is one made by heating 1 7 a polyalkylenepolyamine containing from '2 to 8 alkylene groups with an aliphatic dicarboxylic acid or an amideforming derivative thereof, followed by reaction with epichlorohydrin and acidification.

16. Process according to claim 1, in which the aliphatic polyamine-epichlorohydrin resin is one made by reaction of a polyalkylenepolyamine containing from 2 to 8 alkylene groups with a stoichiometric deficit of a monoor poly-1,2-epoxide, followed by reaction with epichlorohydrin and by acidification.

17. Process according to claim 1, in which the ratio of the polythiol to the polyamine-epichlorohydrin resin is from 7.5 to 25:1 by weight.

18. Process according to claim 1, in which the polythiol is applied from aqueous medium by exhaustion at a temperature between 20 C. and 100 C.

19. Process according to claim 18, in which the polythiol is applied from aqueous medium by exhaustion at a temperature of up to 50 C.

20. Process according to claim 1, in which the polythiol is cured at a pH in the range 7 to 9.

UNITED STATES PATENTS 3,677,693 7/1972 Robinson et al 8127.6 X 3,247,048 4/1966 Gaertner 117-161 UA X 3,580,701 5/1971 Wray et al. 8127.6 3,258,495 6/1966 Le Fave et a1. 260-79 X RICHARD D. LOVERING, Primary Examiner US. Cl. X.R. 

